US2605248A

US2605248A - Heat-curable mixtures of butadieneacrylonitrile copolymers and phenol-aldehyde resins and method of making

Info

Publication number: US2605248A
Application number: US172629A
Authority: US
Inventors: Charles F Fisk
Original assignee: United States Rubber Co
Current assignee: Uniroyal Inc
Priority date: 1950-07-07
Filing date: 1950-07-07
Publication date: 1952-07-29
Anticipated expiration: 1969-07-29

Description

J "This invention relates to an improvement in Patented July 29, 1952 ,1 UNITED STATES HEAT-CURABLE MIXTURES 'OF 'BUTADIENE- ACRYLONITRILE COPOLYMERS AND PHE- :NOL-ALDEHYDE 'MAKING "Charles F. Fisk, Clifton, J., assignor to United :K-ESINS AND IVIETHOD OF States Rubber Company,,Ne'w York, N. 1 a I corporation of New Jersey Y J No Drawing. ApplicationJuly 7 19-50,

Serial N0. 172,629

compositionsot matter comprising heat-curable and heat-cured mutually compatible mixtures of phenol-aldehyde'resins and butadiene-ac'rylonitri'le elast'omers. More particularly the'invention :relates to a new technique discovered by me wherebyithe rate Of hardenin'g or curing of such 12-Claims. (Cl.,20043.)

' amylphenols, diis'opropylphenols; p-tertiary-buj 'tylp'henol, p-phenylphenol, resorcinol, and hymixtures is greatl'y accelerated and a cured prod- I uct "having greatly improved modiilusand resistance to 'c'reep at elevated temperatures is =obtained; II I Much research Work has been done in recent years on thermoset products based upon mutually compatible mixtures of butadiene-acrylonitrile rubbery copolymers and soluble, fusible phenolaldehyde resins. It has'been customary to add hexamethylenetetramine during the formulation-of such mixtures to, provide a source of formaldehyde for effecting thermosetting of the phenolic resin uponheat curing the mixture.

The present invention isbased upon'my discovery that by incorporating a minor proportion of-boric acid or an -alkali metal or ammonium salt of a boric-or a polyboric-acid in .such mixtures before curing, the rate of cure is considerably accelerated and the cured product mani- "fests a considerably improved modulus and re- 'sistance to creep at elevated temperatures, e. g.,

at 100 C. to 150 C.

In, practicing my invention 1 generally 1 employ a phenol-aldehyderesin'which' is soluble, fusible andcapable of'cross-linkingwith formaldehyde,

or a material supplying formaldehyde, such as paraformaldehyde :or hexamethylenetetramine, under the conditions 'of curing. The phenolic resin is almost invariably of the type known in the art as,;a novolak, prepared :by the condensation of phenol and. formaldehyde in the presence of an-acld catalyst, the ratio of phenol to formaldehyde being such that the resin is fusible and soluble in polar solvents. .Thelr'esin'maybe a-gstraight phenol-aldehyde resin or it may be modifiedwith any suitable modifyingagentaccording to known practice. I

Thus, the resin can be based upon common triiunctional phenols, e. g., ordinary phenol. The trifunctional phenols are those which are free droquinone. "I especially prefer to employa resin based upon ordinary phenol and the phenol which is obtained 'from cashew nut shell oil by heating whereby it is converted to the long-chain unsaturated phenol -m-(7-tetradecenyl) phenol cemmonly known as cardanol. When a mixture of ordinary phenol and cardanol is reacted with formaldehyde in a mannerwell known to the art, there is produced a soluble, -fusible, cashew nut shell oil-modified resin which, upon being heated with a minor proportion of hexamethylen'ete'tramine, is converted to the insoluble, in-

fusible state. The amount of the cashew nut shell oil phenol employed for-mod-ifying the resin preferably'ranges iro'm 3'to 12 mol percent'based on the' two phenols. i

Ciashew nut shell oil modifiedphenol-aldehyde resins which; are extremely satisfactory for use in the present invention are available commercially. .Aniexampleof such aresin is thatknown .in -the trade as Durez .No. 126863 Another example is rDurez 12687, which is a mixture of 92- 94 :parts of Durez 12686 and 68-par'ts 0f hexarneth- 'ylenetetramine. ISuch resins are typically made -byheatingithe phenols and the aldehyde, typically formaldehyde, :inl the presence of an acidic catalyst, be. g:, sulfuricor hydrochloric acid to an oil-soluble stage. lDur'ing the'final stageof the resin-forming reactionthe resiniis advanced to thedesired state atwhich it is still reactivewith ihexamethylenetetramine to the insoluble, infusible condition, and "volatile materials are 'removed therefrom, these objectives" being accomplished by passing superheated steam through the charge until the residual mixture hasreached 1' a 'suitabl'eelevated temperature, l'e.::g.,;1 50 Crto from substitution in the three positions ortho V and para tothe phenolic hydroxyl group. The resin can be modified by employing such a trifunctional phenol in conjunction with another phenol which may; be triiunctional, difunctional or-monofunctional. For example, I can use a resin based upon ordinary phenol but modified or co-condense'd with'a lesser proportion of any of the following phenols, which may be either. pure or mixed: th'ezcresols, the xylenols,theitrimethy1- phenols, monochlorophen'ols, dichl'or'ophenols, di-

The elastomeremployed in the practice off my inventionisa butadiene acrylonitrilerubbery cofpolymer of known typev having a combined acrylonitrile content ranging between .10 and :55 molpercent. :Exampl'es :areithe commercially available materials known; as;Per.bunan .18, .Perbunan 26,'Perbunan-35,, I-IycarvOR-l5 andHycar GHQ- 25; The rubbery .copolymer used should bemu tually compatible with the phenolic :resin. 7

The resinshould be" soluble. in the rubbery co polymer at least to the extent of 10% and preierably at least to the extent of on thezw'eight of the copolymer. 'Oneskillediin .the art can readilydetermine whether a 'given resin and a given'rubberycopolymer have the necessary degree of mutual solubility; The mutual solubility can berreadilyjudged by observing the transparenty of themixture :before curing.

The relative proportions of the phenolic resin the resin and the elastomer in one and the rubbery copolymer can vary from 20 to 70% by weight of the resin and correspondingly from 80 to 30% by-weight of" the rubbery copolymer, these proportions being based upon the sum of the resin and the rubbery copolymer,

the resin. Hexamethylenetetramine is by far the."

preferred material for this purpose since it is 40% of the rubbery temperatures;

.low creep at elevated temperature are desirable capable of giving oiT formaldehyde under the.

conditions of curing whereby the resin is advanced to the insoluble, infusible condition. I

can also use formaldehyde, or any of the polymeric formaldehydes such as paraformaldehyde, in conjunction with ammonia or an ammonium salt such as ammonium carbonate as the hardening agent, since such procedures will lead to the formation of hexamethylenetetramine in situ and therefore in efiect amount to the addition of hexamethylenetetramine.

The mutual compatibility, or the solubility of another, should be such that afterthe curing with the hexamethylenetetramine is completed, the condensed cross-linked resin still resmains dissolved in the rubber. Again this can be judged by the transparency of the cured mixture. Thus the cured product can be visualized as a normally cross-linked phenolic resin which however is swollen by a high-molecular-weight, non-volatile solvent and plasticizer, namely, the rubber.

In accordance with the present invention, there is incorporated with themixture, before curing, a compound selected from the group consisting of boric acid and the alkali metal and ammonium salts of boric acids. As used in this specification and in the :claims, the expression salts of boric acid denotes the salts of boric acid proper, i; e., orthoboric acid, H3303, as well as the salts of the related or derivative boric acids namely metaboric acid, H302, and polyboric acids such at tetraboric acid,'H4O7. Thus I can use ammonium borate, which usually is assigned the formula NHiHBiOv, and which is commonly made by bringing together ammonia in the form of ammonium hydroxide and boric acid. In the practice of the present invention ammonium borates analyzing from 6 to 13% of ammonia are generally used. Examples of alkali metal salts of boric acids which can be used in myfinvention are sodium. metaborate (NazB2O4) and sodium tetraborate (118123407); The corresponding potassium salts can be used although they are more expensive. As previously indicated, instead of using the salts, I can use boric acid itself.

The amount of the boric acid or alkali metal or ammonium salt of a 'boric acid used the practice of my invention may vary widely but will seldom be outside of the limits of from 0.5 to 10% by weight based on the sum of the phenolic resin and the butadiene-acrylonitrile rubbery copolymer. Generally the proportion used will not exceed 5% of the weight of resin and rubber.

After the mixture of the resin, rubber, hardening agent, filler if desired, and boric'acid or salt thereof has been prepared, using any method of incorporation which will give a uniform homogenous mixture, this mixture is subjected to curing which is done in the conventional manner, namely by heating at an elevated temperature until the curing reaction is completed.

From the physico-chemical point of view, the best and most convenient way .of; measuring the state of cure or degree of polymerization or condensation is measuring the modulus at 100 C. or at some higher temperature. This is preferable to. measuring the modulus at room temperature because afterthe cure has advanced to a certain point, further condensation does not greatly change the modulus at room temperature but does strongly increase the modulus at elevated Ingeneral, a high modulus and as long as these are attained in a way which is consistent with meeting the other engineering requirements. The curing is generally done at a temperature of at least 300 F. The temperature can range upwardly from this value to a point at which thermal decomposition of the mixture or of some component thereof would take' place to an objectionable extent. i f

The following data-show how the advance in the cure of a typical mixture of phenolic resin and butadiene -acrylonitrilejrubbery copolymer is reflected in an increase1'in;modulusf :a decrease in creep factor. ,Herethe compound contains no accelerator other thanhexamethylenetetramine, which, although it is oftenmisena'med an accelerator, is not truly an accelerator; "The zinc stearate is used merely as a mold release agent. r

Formulation:

Hycar OR'15.. arts by weight. 100 Durez 12687".-. do -100 Diatomaceous earth- .d 100 Zinc stearate. do: 2

Mold cure temperature .IF. 330

Mold cure pressure p. s; 1.. 300

' Modulus, (p. s. l.)X10 Cree Factor at- Minutes-Cure p Time The modulus is exp'ressedto correspondto the usual engineering'flexura1 modulus lbs. per square inch. Actually, the modulus is tested in torsion using the apparatus, procedure, and calculation method described by Clash and Berg, Industrial and.Engineering Chemistry 34, 1218 (1942)."

When phenolic gum plastics are subjected to deformation they exhibit creeps For this reason, modulus is calculated based "on the deformation (D10) observed after the load has been applied for 10 seconds. .To indicate the creep tendency a deformation (D) is also "observed after the load has been applied f r. 100 seconds, and the dimensionless ratio is arbitrarily called the"creep factor.

r In accordance with the present inventionfthe addition of5' parts of'ammonium borate greatly accelerates the rate of cure; In other words, the modulus of the cured product at100 C. for' a given time of cure is considerably higher when the ammonium borate is present. This is shown by Tables Ia and II) which give. the modulus of compounds cured for various" lengths 'of 'time with and without'5 parts of aminonium'borate.

The ammonium borate used in'Tables Ia through VI analyzed 6.5 of ammonia but other bor'ates of various ammonia contents would serve aswell. In Table lathe volume loading'of three different'fillers is kept constant while th I-Iycar/Durez Weight ratio is kept fixed at 1:1. In Table II) the ratio of I-Iycar to Durez is varied, while the volume loading of one filler (-Dicalite) is kept constant.

ltwill'be' seen fromTables 1a and ID that fora given time of cure the modulus" at 100 C. is approximately doubled by the presence of the borate. This efiect is obtained whether the filler be wood flour, carbon black, clay or diatomaceous earth, and whether the resin-to-rubber ratio is 67/100, 100/100; 01'150/100. I

Table H gives'some' ot th physical properties measured on the compounds of Table I.

i Physical properties "obtained with "and without borate present Q- .q Cure 2 5 C. mpac A S hear Mixture in Amm Shore t Strength H at Modulus... Strength Table I Borate F D S. L) XHH ftitgvgl s 1 notch AMMONIUM BORATE AS A CURE, ACCEL- ERATOR AS SHOWN BY MODULUS AT mo e. r

I TABLE 1A Base formulation:

Hycar OR-15 100 grams Zinc stearate 2 grams Durez 12687--- 100 grams er 20 cos/100 g. rubber and resm Ammonium borate or -grams as shown Mixture A B C 50 Parts by 72 Parts by 104 Parts by Weight Wood l Weight Carbon Weight Suprex Cure at Flour Black Clay .1

With Without With Without With Without Borate Borate Borate Borate Borate I Borate 1 3'2 26 11 3s 14 1 34 18 31 14 .45 20 1 39 I34 20 v 51 26 Figures show modulus at 100 C. in thousands of p. s. i. The higher the modulus the more complete is the degree of polymerizetion or cure.

TABLE 113 Base formulation: I

Hycar OR-15 100 grams Zinc stearate---- 2 grams Durez 12687.... -As shown Diatoinaceo'us earth (Dica11te).- 78, '93 or 116 (20 cps/100 g. rubber and resin) Ammonium borate 0 or 5 as shown Mixture D E F 67 Parts Durez I 100 Parts Durez 150 Parts Durez 12687-48 Parts 1268793 Parts 12687' 116 Parts Cure Diealite Dicalite Dicaltte 330 F.

With Without With Without With Without Borate v Borate Borate Borate Borate Borate Table III s ows tr e improvement in modulus and creep faster-at150 C. "of some of the mix-' 1\ /Iod11 lus at I Creep Factor at 150 0. 150 0. Mixture in Table I .ggsix .1 f 7 1 With w With ,alou- 1 ..'0u V Borate Borvater Borate v Borate 5" V '1 l0 2. 5 1.75 .1. 73 A 10' 1 25 4. 1 v 1. 65 '1. 72 30'; 1 29 14 l. 46 l. 56

5' f 18' 3.1 1:65 1. 96 B 10" 121 3.8 1. 59 1. 79 30' 33? 7. 2 l. 38 1. 76

q 5 1 19 2. 8 1. 65 1. D -1" 10" 26 4I7' 1.54 1.82 30 :34: "9:5 1.37 1.75

1 Figuresshow modulus at 150Cjin thousands bfp: s. i. The higher the modulus the more-complete 1S thedegree oi-polymerization or cure.

Table IV shows that the same results are obtained whether the commercial resin Durez1'2686 or a laboratory phenolic resin is employed. In Examples G and H, reported in Table IV, the laboratory phenolic resin used was made as follows:

A mixture of 9.5 mols of ordinary phenol, 0.5 mol of cardanol sold as Cardanol 923; by the Irvington Varnish Company, 8.0 mols of formaldehyde (added gradually) and 0.12 mol of HCl in water'was heated for three hours at C., after which the water was removed by heating the'mixture; underreduoedpressure, to about 160 C. The resin obtained was soluble in alcohol, sintered at 82 C., and when mixed with 7% hexamethylenetetramine had a gel time of about 1 minute at 300 v r TABLE IV Effect of ammonium borate COMPARISON or A LABORATORY PHENOLIC WITH DUREZ 12686 Mixture G H I J Hycar OR-li. 100 100 100 100 Laboratory Phenolic Resin 93 93 Durez 86.. 93 93 Diatomaceous Earth 93 93 93 93 Zinc Stearate 2 2 2 2 exa 7 7 7 7 Ammonium Borate. 5

TCure me at G H I J 330 F 100 Modulus: 31 ff fi 1}, 3,} ")XIM so 26 42 23 4o 5 1.69 1. 42 1. 78 1. 47 100 C. creep Factor-un 10 1.70 1. 43 1. 60 1. 38 1. 66 1. 34 Q- Modulus 18 "if -331 23 iii ")Xlw so 139 138 140 137 5 1. 1. 15 1. 17 1. 15 C. Creep Factor--. 10' 1.15 1. 15 1. 18 1. 16 1. 16 1.13

Table V shows that the 100 C. modulus of a cured product containing ammonium borate as the acceleratoris not afiected by boiling in water. Cured samples with and without borate accelerator were boiled for two hours in water, which caused absorption of 1.5% of water. The samples were then dried and tested for modulus and creep factor at 100 C. The sample obtained from. mixture A2 still showed approximately twice the modulus of the sample obtained from mixture A1. Under the conditions of the boiling water test there was accordingly no disintegration or weakening of the internal structure of the thermoset resin, whereas it is well known that anonsetting hydroxylic resin which has been borated, such as borated polyvinyl alcohol complex, is very readily hydrolyzed, with disintegration of the structure.

- TABLE V Compounds cured with borate are not afiected by hot water Mixture A1 A2 Hycar OR-15 100 100 Durez 12687 100 100 Wood Flour 50 50 Zinc Stear 2 2 Ammonium Borate 5 Cure at 3 330 F. X Y X Y 1 v 5' 15 16 a2 33 100 C. Modulus (p. s. 1.) X101. 10 18 19 34 34 r 30 25 25 89 40 5 1. 76 1. 57 1. 51 l. 43 100 C.Creep Factor 10 1. 59 1. 52 1. 48 1. 37 30 1. 50 .42 1. 42 1.35

Treatmentr X: Original sampl Y: Sample boiled 2 hours in water, then dried 2 days at 25 C.

Applicant conducted other experiments which showed that the addition of 5 parts of several other ammonium salts, namely, the carbonate,

thiosulfate, and thiocyanate, had no efiect whatever on the rate of cure of the mixtures with Y which the present invention is concerned.

TABLE VI Comparison of ammonium borate, sodium borate, and boric acid as cure accelerators Mixture K L M N 0 P Hycar OR-l5 100 100 100 100 100 100 urez 12687 100 100 100 100 100 100 Diatomaceous Eartl1-- 93 93 93 93 93 93 Zinc Stearate 2 2 2 2 2 2 Ammonium Borate. 5 10 Sodium Borate (bora 7 Boric Acid 1.2 5

Cure 5 K L M N 0 P 100 O. Modulus 5 8 31 34 19 15 27 i 10' 13 34 35 25 2o 26 e r Creep 5' 1. 86 1.47 1.47 1.58 1.70 1. 51 10 1. 64 1. 43 1. 46 1. 49 1. 70 1. 52

From Table VI it will be seen that ammonium borate, borax, and boric acid behave in a similar manner in accelerating the cure of the mixtures with which the present invention is concerned. It will also be seen that the use of 10 parts of ammonium borate gives the same results as five parts thereof.

The present invention provides three important advantages over common practice. First, it permits cures to be completed or advanced to a given degree in a shorter time than usual. Secondly, it provides cured products having a modulus at C. or over which is substantially higher than normal. Thirdly, it substantially reduces the rate of creep under load at high temperatures. This improved resistance to heat softening is highly desirable in applications of thermoset phenolic resin-rubber products for high temperature service, such as gaskets, plating barrels, motor slot insulation, chemical pipe, oil-less bearings, filter plates, silent gears, etc.

A distinction must be made to show the advantages in resistance to heat-softening obtained by the present invention. It is apparent that if a high modulus at 100 C. is required, it can readily be obtained in an ordinary phenolic resinrubber composition by using a high resin-torubber ratio, a high filler loading, or both. The drawback to these'methods is that both of them increase the hardness and modulus at room temperature which, in most cases, is quite undesirable because brittleness, i. e., tendency to break upon impact, is greatly increased. However, by the use of boric acid or its salts in accordance with my invention, there is obtained a product which has superior high temperature modulus and creep resistance in combination with a given room temperature hardness and impact resistance which are established in advance by appropriate selection of resin content and filler loading.

Having thus described my invention, what I claim and desire to protect by Letters Patent is:

1. A composition of matter comprising a mixture of a soluble, fusible, phenol-aldehyde resin, hexamethylenetetramine as a hardening agent therefor, a butadiene-acrylonitrile rubbery copolymer, said resin and said rubbery copolymer being mutually compatible, and an accelerator composed of a compound selected from the group consisting of boric acid and the alkali metal and ammonium salts of boric acids.

2. A composition of matter comprising a mixture of a soluble, fusible, cashew nut shell oilmodified phenol-aldehyde resin, hexamethylenetetramine as a hardening agent for said resin, a butadiene-acrylonitrile rubber copolymer, said resin and said rubbery copolymer being mutually compatible, and an accelerator composed of a compound selected from the group consisting of boric acid and the alkali metal and ammonium salts of boric acids.

3. A composition of matter comprising a mixture of a soluble, fusible, phenol-aldehyde resin, hexamethylenetetramine as a hardening agent for said resin, a butadiene-acrylonitrile rubbery copolymer, said resin and said rubbery copolymer being mutually compatible and being present in relative proportions ranging from 20 to 70% by weight of said resin and correspondingly from 80 to 30% by weight of said rubbery copolymer based on the sum of said resin and said rubbery copolymer, and from 0.5 to 10% by weight based on the sum of said resin and said rubbery copolymer of an accelerator composed of a compound selected from the group consisting of boric acid and the alkali metal and ammonium salts of boric acids.

4. A composition of matter comprising amixture of a soluble, fusible, phenol-aldehyde resin, hexamethylenetetramine as a hardening agent for said resin, a butadiene-acrylonitrile rubbery copolymer, said resin and said rubbery copolymer being mutually compatible and being present in relative proportions ranging from 40 to 60% by weight of said resin and correspondingly from 60 to 40% by weight of said rubbery coploymer based on the sum of said resin and said rubbery copolymer, and from 0.5 to 10% by weight based on the sum of said resin and said rubbery copolymer of an accelerator composed of a compound selected from the group consisting of boric acid and the alkali metal and ammonium salts of boric acids.

5. A composition of matter comprising a mixture of a soluble, fusible, cashew nut shell oilmodified phenol-aldehyde resin, hexamethylenetetramine as a hardening agent for said resin, a butadiene-acrylonitrile rubbery copolymer, said resin and said rubbery copolymer being mutually compatible and being present in relative proportions ranging from 40 to 60% by weight of said resin and correspondingly from 60 to 40% by weight of said rubbery copolymer based on the sum of said resin and'said rubbery copolymer, and from 0.5 to 10% by weight based on the sum of said resin and said rubbery copolymer of an accelerator composed of a compound selected from the group consisting of boric acid, and the alkali metal and ammonium salts of boric acids.

6. A composition as set forth in claim wherein said com ound is ammonium borate.

7. A composition as set forth in claim 5 wherein said com ound is sodium tetraborate.

8. A composition as set forth in claim 5 wherein said compound is boric acid.

9. A heat-cured composition of matter comprising a mixture of a, soluble, fusible, phenolaldehyde resin, hexamethylenetetramine as a hardening agent therefor, a butadiene-acrylonitrile rubbery copolymer, said resin and said rubbery copolymer being mutually compatible, and an accelerator composed of a compound selected from the group consisting of boric acid and the alkali metal and ammonium salts of boric acids.

10. A heat-cured composition of matter comprising a mixture of a soluble, fusible, cashew nut shell oil-modified phenol-aldehyde resin, hexamethylenetetramine .as a hardening agent for said resin, a butadiene-acrylomtrile rubbery copolymer, said resin and said rubbery copolymer being mutually compatible and being present in relative proportions ranging from 40 to 60% by weight of said resin and correspondingly from 60 to 40% by weight of said rubbery copolymer based on the sum of said resin and said rubbery copolymer, and from 0.5 to 10% by weight based on the sum of said resin and said rubbery copolymer of an accelerator composed of a compound selected from the group consisting of boric acid, and the alkali metal and ammonium salts of boric acids.

11. The method which comprises heating at a curing temperature of at least 300 F. a mixture of a soluble, fusible, phenol-aldehyde resin, hexamethylenetetramine as a hardening agent therefor, a butadiene-acrylonitrile rubbery copolymer, and an accelerator composed of a compound selected from the group consisting of boric acid and the alkali metal and ammonium salts ofboric acids, until said mixture is cured and said resin is converted to the insoluble, infusible state, the presence of said compound considerably accelerating the rate of curing and giving a cured product having considerably improved modulus and resistance to creep at elevated temperature as compared to a similar mixture without said compound.

12. The method which comprises heating at a curing temperature of at least 300 F. a mixture of asoluble, fusible, cashew nut shell oil-modified phenol-aldehyde resin, hexamethylenetetramine as a hardening agent for said resin, a butadieneacrylonitrile rubbery copolymen and an accelerator composed of a compound selected from the group consisting of boric acid and the alkali metal. and ammonium salts of boric acids, until said mixture is cured and said resin is converted to the insoluble, infusible state, the presence of said compound considerably accelerating the rate of curing and giving a cured product having considerably improved modulus and resistance to creep at elevated temperatures as compared to a similar mixture without said compound.

CHARLES F. FISK.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,156,124 Novotny Apr. 25, 1939 2,459,739 Groten et al. Jan. 18, 1949 2,532,374 Shepard et al Dec. 5, 1950 OTHER REFERENCES Shepard et al., Modern Plastic, Oct. 1946, pp. 154456, 210 and 212.

Claims

1. A COMPOSITION OF MATTER COMPRISING A MIXTURE OF A SOLUBLE, FUSIBLE, PHENOL-ALDEHYDE RESIN, HEXAMETHYETETRAMINE AS A HARDENING AGENT THEREFOR, A BUTADIENE-ACRYLONITRILE RUBBERY COPOLYMER, SAID RESIN AND SAID RUBBERY COPOLYMER BEING MUTUALLY COMPATIBLE, AND ACCELERATOR COMPOSED OF A COMPOUND SELECTED FROM THE GROUP CONSISTING OF BORIC ACID AND THE ALKALI METAL AND AMMONIUM SALTS OF BORIC ACIDS.